Resinous composition and method of forming the same



Patented Mar. 6, 1934 UNITED STATES PATENT OFFICE Arthur S. Ford, NewYork, N. Y., assignor to Industrial Sugar Products Corporation,

New

York, N. Y., a corporation of Delaware No Drawing. Application June 10,1931, Serial No. 543,488

19 Claims.

This invention relates to a process for the formation of a novelresinous composition, and the composition of matter thereby formed.

According to the invention, the process is sus- 6 ceptible of numerousvariations in the quantities and character of the ingredients involved,and these variations of the process produce products of differingcharacteristics which have various uses in the arts.

One of the objects of the present invention is to produce a plasticresin resulting from the condensation or reaction of phthalic anhydridewith the reaction product of a saccharide such as sugar and an aldehydesuch as formaldehyde or a substance capable of producing formaldehyde.The condensation or reaction product thus formed is capable of beingpoured into molds and rapidly setting therein as a hard brilliantplastic substance whose color varies with the degree and extent of theheating to which the solution of formation has been subjected, and whichis insoluble in water but soluble in organic or spirit solvents, and maybe used as a molding powder.

A further object of the invention is to produce, according to anotherform thereof, a baking lacquer or enamel of dark color, great strengthand covering qualities, and completely impervious to water.

Other objects and advantages and uses of the invention will appear fromthe description thereof which is given below.

This application is a continuation in part of my pending applicationSerial No. 384,230, filed August '7, 1929, for Synthetic resins.

In an application filed by me on even date herewith and identified as S.N. 543,484, I describe and claim a resinous or adhesive substance madeby the condensation or reaction together of a saccharide such as sugarand an aldehyde such as formaldehyde in aqueous solution.

In an application filed by me on even date herewith and identified as S.N. 543,485, I disclose and claim a water-insoluble resinous substancemade by the condensation or reaction together of an anhydrous saccharidesuch as sugar and an anhydrous aldehyde such as paraformaldehyde.

In two other applications filed by me on even date herewith andidentified as S. N. 543,486 and S. N. 543,487, I disclose and claim acomposition of matter made by the reaction of urea or organic acids withthe reaction product of a saccharide and an aldehyde.

It is a feature of the present invention that a saccharide is firstcondensed or reacted with an aldehyde, and the resultant condensationproduct, either with or without the addition of a hardening agent, iscondensed or reacted with phthalic anhydride. The final condensationproduct so obtained, according to the invention, may be nearlywater-white, or a light golden yellow, or any darker shade to a jetblack, depending upon the manner and extent of heating after theaddition of phthalic anhydride.

A further feature of my invention resides in the method by which thesecond stage of the reaction, or second condensation, is carried out inorder to avoid explosive destruction of the apparatus.

A further feature of my invention resides in the production of a varnishor baking lacquer by the solution of the product of the second stage ofcondensation, above referred to, in a suitable organic or spiritsolvent, and the application of this solution to a surface to belacquered or enameled, and if desired the baking thereof to drive offmore completely the organic solvent and to drive still further towardcompletion the final stage of condensation to produce an enamel of greathardness and permanence, and substantially impervious to water.

In accordance with one form of the present invention a saccharide, or asubstance containing a saccharide including particularly but not by wayof limitation, cane sugar, invert sugar, glucose,

saccharose, levulose, molasses (for the production of a dark brown orblack resin or adhesive) or chopped sugar cane which has not been freedof sap (for the production preferably of opaque filled resinous masses)or other monoor disaccharides, is caused to react with a reagent such asan aldehydic substance or a substance capable of producing an aldehyde,such as formalin, paraformaldehyde or oxymethylene, furfural, orformaldehyde gas, or with an aromatic amine, such as anilin oil. Any oneof the saccharides mentioned may be used singly, or two or more of thesame may be mixed. Any one of the reagents named above for reaction withthe saccharides may be used singly, or two or more thereof may be mixed.The reaction takes place in the presence of a suitable solvent, the useof water being preferred in the practise of the invention.

In accordance with another form of the invention an anhydroussaccharide, such as refined cane sugar, anhydrous invert sugars,anhydrous glucose, or other monoor disaccharides from which water ofsolution (as distinguished from water of crystallization or chemicallyconstituent water) has been expelled, is heated slightly above themelting point thereof until it is brought to a fluid condition withoutsubstantial carameliza- 110 tion or charring, and in this fluid is thendissolved a suitable amount of an anhydrous aldehyde such as thecrystalline polymer of formaldehyde, known as paraformaldehyde oro-xymethylene, or formaldehyde gas is bubbled through the fluid. Any oneof the saccharides mentioned may be used alone, or two or more may becombined. Any one or more of the aldehydes may be used alone, or two ormore may be combined. The reaction between the anhydrous saccharide andthe anhydrous aldehyde may be carried out under pressure in an autoclaveso that air is prevented from coming into contact with the reactingmixture.

In the examples which are set forth below I have indicated exactquantities of materials which may be used in the successful carrying outof this invention, but these are illustrative only as the quantitiesinvolved may be varied within considerable limits to produce substanceshaving different physical characteristics. I have found that a largeamount of the aldehyde or equivalent substance in excess of thequantities stated in the examples is not harmful, as the excess appearsto be driven off upon heating. On the other hand, an excess of thesaccharide produces a'resin which remains sticky and tacky on its outersurface and will not harden properly.

I do not know the nature of the reaction which takes place between thesaccharide and the aldehyde, but it would appear that the sugar is fullyconsumed as the reaction mass which is produced does not have theordinary physical characteristics of sugar, nor does it have most of thechemical characteristics thereof though it will rotate the plane of"transmitted light.

Inasmuch as the reaction between the sugar and the aldehyde preferablyoccurs without caramelization of the sugar, the reaction will take placebelow 100 C. when dry sugar and a dry aldehyde are used, and will takeplace below caramelization temperature when water is present as in caseof the use of formaldehyde gas dissolved in water. Accordingly, areference herein to a substance capable of producing an aldehyde isintended as a reference to a substance which will yield an aldehyde atthe reaction temperature, e. g., at temperatures in the neighborhood of100 C. to 150 C.

Upon completion of the preliminary condensation or reaction between thesaccharide and aldehyde, there is then added to the resultant reactionmass in the vessel a suitable quantity of phthalic anhydride in a numberof small quantities at intervals with constant stirring or agitation ofthe liquid between installments in order to insure the complete solutionand absorption of each installment before the addition of a subsequentinstallment.

I have'found that the addition of the entire amount of phthalicanhydride at one time will produce a reaction of explosive violence, butapparently no chemical detriment is produced if the apparatus is sodesigned and constructed as to be able to withstand the effect of thesudden genaration of pressure. Accordingly, while no chemical detrimentappeals to flow from the ad dition of the entire amount of phthalicanhydride at one time, convenience in manipulation makes it preferableto introduce the same in a number of small installments with constantstirring and agitation so that the violence of the reaction dissipated.

The amount of phthalic anhydride employed may be varied within widelimits, depending upon the hardness, water-resistance and color of theproduct which it is desired to obtain. The quantity of phthalicanhydride may be varied from 50% to 150%, by weight, of the saccharideoriginally employed, and it is probable that the quantities can bevaried within wider limits than those stated without obtaining asubstantially diilerent product or departing from the invention.

Heating is employed during the initial condensation reaction of thesaccharide and the aldehyde. As the temperature of the heating vessel israised there is a slow evolution of gas. When the temperature has beenraised suificiently to cause the condensation reaction to take placethere is a sudden strong evolution of gas. Thereafter, though thetemperature be substantially raised, there is no further substantialevolution of gas, though if the reaction be carried out in aqueoussolution there will be a slow elimination of water vapor. Afterthis'initial condensation has taken place there is a noticeable changein the physical characteristics of the contents of the heating vessel,including especially the elimination of any tendency to caramelize onincrease of temperature above the caramelizing point of sugar which isabout'100 C.

After the first condensation reaction has been completed, the phthalicanhydride is then added. This is added in a succession of smallinstallments in accordance with the foregoing description, and duringthe addition of the phthalic anhydride the liquid is maintained at asuitably elevated temperature to promote rapid absorption of thephthalic anhydride. This can be effectively accomplished at atemperature of about 180 C.

After the phthalic anhydride has been added; and if theinitial reactionwas carried out in aqueous solution, it is necessary to heat further todrive off water vapor. If this is carried out at relatively hightemperatures, such as 200-300 0., there will be bubbling and frothingand as the heat is continued the solution will gradually change from aclear and water-white appearance to a light amber or golden yellow, andthen successively through darker shades until it will become, if keptlong enough at these high temperatures, dark brown or jet black. In thisway it is possible to produce a resinous substance which is dark brownor jet black in color, and which will produce a varnish or bakinglacquer of the same color.

If it is desired to produce a plastic substance of light color, orsubstantially colorless, this can be accomplished by maintaining thetemperature of the solution, after addition of phthalic anhydride, at atemperature slightly less than the boiling point of water, i. e., about90 C. for a somewhat long period of time. In this way most of the watervapor can be expelled (if water vapor was originally present) withoutsubstantial discoloration of the solution.

Accordingly hardness and water-resisting qualities of the end productcan be increased by increasing the percentage of phthalic anhydrideemployed. At the same time color can be controlled by temperaturecontrol, that is, heating the reaction rnass after addition of thephthalic anhydride to a relatively high temperature will promote thegeneration of color within the reaction mass and omission of suchheating (i. e., heating only to, say 90 C. to drive off water vapor ifpresent) will preserve the substantially water-white characteristics ofthe reaction mass.

properties and is water-insoluble.

The addition of phthalic anhydride to the solution in which saccharideand the aldehyde have condensed, appears to give rise to a second stageof condensation or reaction. After the phthalic anhydride has beenreacted or condensed with the substance already in the vessel, and ifnecessary after water vapor has been eliminated, the fluid is then readyto be poured into molds. It is a noticeable difference between theprocess of this invention and the process set forth in my applicationsS. N. 543,486 and S. N. 543,487, that cooling effects immediatehardening of the reaction mass in the present invention, whereas in theapplications referred to, wherein urea and various organic acids areemployed, increased viscosity and loss of pouring quality appear to bebrought about by continuing the heating and cooling will preserve theability of the mass to be poured till further heated.

Upon pouring into molds and cooling, the reaction mass of this inventionsets rapidly into a hard brittle crystalline substance which breaks witha sharp brilliant fracture, is transparent (unless heating has beencarried to an extent sufliclent to raise a high coloration) and isinsoluble in water though soluble in organic or spirit solvents.

The cooled and hardened reaction mass of this invention may bepulverized or broken up to form a useful molding powder. This moldingpowder has the useful characteristic that it will keep indefinitely inthe open air and not lose its useful qualities. It has a variety offields of usefulness either alone or as a binder to be incorporated withsuitable inert fillers in the preparation of tough durable moldedarticles which may have a wide range of properties depending on theingredients selected. Thus, opacity may be obtained by the use of inertfillers such as ground-up synthetic or natural resins or gums, waxes,fats, reclaimed rubber, cellulose nitrate or acetate, or the like, orsynthetic condensation products. Transparency may be obtained by the useof powdered glass wool. Special effects may be obtained by the use ofcolored powdered glass wool, or combinations of powdered glass wool ofdiffering colors. Dielectric strength may be obtained by the addition ofany inert non-metallic substances, including those named above, whichserve to give strength and rigidity to the mass.

This molding powder, being itself water-insoluble, gives the quality ofwater-resistance to all the molded articles of which it forms a substantial part. If desired, however, oils such as castor or linseed oilsmay be added to increase the water-resistance of the molded articles.

The molding powder above referred to, when mixed with the othersubstances mentioned, may be pressed into molds under a pressure of 1000to 2000 pounds per square inch at a temperature of l50-350 C. Thus aresin may be produced, which has high tensile strength, and is capableof being machined, turned and polished. The molded articles made with mymolding powder herein disclosed appear to be very light and have a verylow specific gravity.

The cooled and hardened reaction mass of this invention may be dissolvedin a suitable organic or spirit solvent to form a satisfactory varnishor baking laquer. If the reaction was so controlled as to produce anearly water-white product, it is possible by solution thereof in aspirit solvent to produce a water-white colorless varnish which hassatisfactory covering When painted or sprayed on a surface it may bebaked thereon, if desired, to give a very hard waterimpervious surfaceof high lustre. This baking, if prolonged, will cause the enamel orvarnish to become gradually darker in color, ranging through variousshades from light golden amber to deep brown or jet black.

The following illustrations are set forth by way of example only:-

Example 1.300 gms. of granulated white sugar was dissolved in a vesselin 250 cc. of 36% commercial formalin solution. Heat was applied to thevessel and the contents were stirred until the sugar had dissolved. Thetemperature was then gradually raised taking care not to permitcaramelization of the sugar until a temperature was reached at whichthere was a large evolution of gas and finally, without temperaturereduction, the liquid became quiet. There was then added 10 gms. ofhexamethylenetetramine, with sufficient stirring to get it intosolution. Thereafter the heat was gradually raised to the neighborhoodof 180 C. and there was then added to the solution in ten equalinstallments at intervals of about a minute with constant stirring andagitation, 300 gms. phthalic anhydride. Each installment was sprinkledgently on the surface of the fluid with constant stirring and agitation.The addition of phthalic anhydride produced substantial bubbling whichcontinued for about a minute after the addition of each installment.

After all the phthalic anhydride had been gotten into solution, thetemperature was reduced to 90 C. and maintained there for several hours.After the heating at this temperature, it was found that the water-whitecharacteristic of the reaction mass in the vessel had not materiallychanged. The liquid was now poured into molds and permitted to cool. Itwas found, after cooling. to have set as a brilliant substantiallywater-white non-resilient substance which was somewhat brittle and brokewith a sharp fracture. It was soluble in spirit solvents such asacetone, but insoluble in water.

Example 2.-The process of Example 1 was carried out to the point atwhich the phthalic anhydride had been gotten into solution.

The temperature was now increased from 180 C. to the neighborhood of 250C. and maintained there for several hours. During this time the color ofthe solution steadily darkened and at the end of ten hours the liquidhad assumed a dark brown or blackish color.

This was poured into molds and hardened on cooling to a shinybrownish-black substance which was insoluble in water but soluble inspirit solvents.

Example 3.-225 gms. of granulated cane sugar were placed in an autoclaveand gradually heated with cccasicnal agitation until the sugar hadmelted to a light amber fluid. Without diminishing the temperature therewas then added 100 gms. of solid paraformaldehyde, and the contents ofthe autoclave were agitated until the solution was completed. Thetemperature was then gradually increased and the reaction between thesugar and the formaldehyde was permitted to proceed under self-generatedpressure. When the temperature had reached about 200 C. the pressure wasreleased and there was added 10 gms. of hexamethylenetetramine. Theliquid was sufficiently agitated to get the hexamethylenetetramine intosolution. There was then added 200 gms. of phthalio anhydride in teninstallments or portions with constant agitation. The solution frothedand bubbled noticeably and its color, already amber yellow, deepenedsomewhat.

When the phthalic anhydride had been gotten into solution, the liquidwas at once poured without further heating into molds where, on cooling,it was found to have hardened to a shiny brownish resinous substancewhich was brittle, broke with a brilliant fracture, was insoluble inwater, but soluble in spirit solvents.

Example 4.-The poured substance made in accordance with Example 1, was,after cooling, broken up and dissolved in acetone. It was found to gointo solution readily and the concentration was so adjusted as toproduce a thick viscous paint-like solution. This, being substantiallywater-white, was found to be an excellent crystal varnish which waswaterproof and had good covering properties.

Example 5.-The varnish made in accordance with Example 4 was sprayed ona metal surface and then baked thereon at 300 C. for several hours. Itwas found to have darkened in color to a deep brownish black, and washard, elastic, and tough. It was found to be durable even in thinapplication and was impervious to water.

. In accordance with the-foregoing disclosure, I am able to makea'composition of matter having among others the following properties:

The poured reaction mass made in accordance with my invention, after ithas cooled and hardened, forms a brilliant, somewhat brittle plasticsubstance which, depending on temperature control, may be substantiallycolorless and water-white or may range from light amber to jet black. Itbreaks with a brilliant fracture and its composition on hardeningappears to be uniform. It'is soluble in the usual organic or spiritsolvents such as ether, alcohol, toluol, amyl I acetate and acetone, butis not soluble in or affected by water 'so far as I have been able toascertain. v

This mass, when tory molding powder which will keep satisfactorily inthe open air indefinitely, is inherently water-insoluble and, when madewater-white and colorless, can be usefully employed with various inertfillers mentioned above in the making of many molded articles whoseproperties depend on the nature and proportions of the inert'fillersselected. It is a noticeable characteristic of my molding powder thatits specific gravity is very low, and it is possible in using it to makemolded articles of very low specific gravity.

The hardened reaction mass, when dissolved in a spirit solvent, wasfound to make a satisfactory varnish or lacquer which flowed well, hadgood covering properties, dried quickly to a brilliant and waterimpervious surface, and could be made water-white or any shade fromamber to jet black by suitable control of the heating conditions asabove set forth. When a colorless, or lightly colored, varnish of thiskind was baked it was found that the hardness was increased and theinherent coloration increased. Baking any of the varnishes made inaccordance with my invention improves the permanence andwater-imperviousness.

' Iclaim:

1. The process of making a plastic substance which comprises reactingtogether the product of the reaction of a saccharide of the groupconsisting of monoand di-saccharides and an aldehyde, and phthalicanhydride.

pulverized, forms a satisfac-' '2. The process of making a plasticsubstance which comprises reacting together the product of the reactionof a sugar and an aldehyde, and phthalic anhydride.

3. The process of making a plastic substance which comprises reactingtogether the product of the reaction of a sugar and a substance capableof producing formaldehyde at the reaction temperature, and phthalicanhydride.

4. The process of making a plastic substance which comprises reactingtogether a sugar and a substance capable of producing formaldehyde atthe reaction temperature, and after the reaction is complete adding tothe liquid in a succession of small increments sufiicient phthalicanhydride to cause the reaction mass to set to a hard plastic substanceon cooling.

5. A plastic substance comprising the product of the reaction ofphthalic anhydride with the product of the reaction of a saccharide ofthe group consisting of monoand di-saccharides and an aldehyde.

6. A plastic substance comprising the product of the reaction ofphthalic anhydride with the product of the reaction of a sugar and analdehyde. '7. A'plastic substance comprising the product of the reactionof phthalic anhydride with the product of the reaction of a sugar and asubstance capable of producing formaldehyde at the reaction temperature.

8. A molding powder comprising the pulverized product set forth in claim5.

9. A molding powder comprising the pulverized product set forth in claim6.

10. A molding powder comprising the pulzerized product set forth inclaim 7.

11. The process of making a plastic substance which comprises reactingtogether the product of the reaction of a sugar and formaldehyde, andphthalic acid.

12. The process of making a plastic substance which comprises reactingtogether the product of the reaction of a sugar and an aldehyde, andphthalic acid.

13. The process of making a plastic substance which comprises reactingtogether the product of the reaction of a saccharide of the groupconsisting of monoand disaccharides and an aldehyde, and phthalic acid.

14. The process of making a plastic substance which comprises reactingtogether the product of the reaction of a sugar and formaldehyde, andphthalic acid and heating the reaction mass sufiiciently to cause it toharden.

15. The process of making a plastic substance which compri es reactingtogether the product of the reaction of a saccharide of the groupconsisting of monoand di-saccharides and an aldehyde, and phthalic acidand heating the reaction mass sufficiently to cause it to harden.

16. A plastic substance formed by the reaction of phthalic acid with thereaction mass of a sugar and formaldehyde. 1

17. A plastic substance formed by the reaction of phthalic acid with thereaction mass of a sugar and an aldehyde.

18. A plastic substance formed by the reaction of phthalic acid with thereaction mass of a saccharide of the group consisting of monoanddisaccharides and an aldehyde.

19. A molding powder for use in forming plastic substances comprisingthe pulverized product of claim 18.

' ARTHUR S. FORD.

